KR20210013986A - Antibacterial superabsorbent polymers - Google Patents

Abstract

The present invention relates to an antibacterial phenolic polymer compound introduced to a superabsorbent polymer in order to obtain an antibacterial superabsorbent polymer, and a method for preparing the same. A phenolic compound having an alkyl group is used as a monomer to form covalent bonding with the surface of a superabsorbent polymer (SAP), which results in excellent coating stability to the superabsorbent polymer. In addition, the present invention relates to a superabsorbent polymer (SAP) and a method for preparing the same. Particularly, the SAP surface is modified with the antibacterial phenolic polymer material so that the SAP may have excellent antibacterial activity and maintain excellent absorption property of the SAP itself, even after coating. Further, the present invention relates to a hygienic article using the antibacterial superabsorbent polymer to provide improved quality.

Description

Antimicrobial super absorbent polymer {ANTIBACTERIAL SUPERABSORBENT POLYMERS}

The present invention relates to a super absorbent polymer, and in particular, to an antibacterial super absorbent polymer to which antibacterial properties are imparted due to surface modification.

In addition, the present invention relates to an antimicrobial polymer compound introduced into a superabsorbent polymer to prepare an antimicrobial superabsorbent resin, and in particular, to an antibacterial phenolic polymer compound having phenol and alkyl functional groups and exhibiting antibacterial action in a contact manner.

Due to the surface modification of the superabsorbent polymer using the antimicrobial polymer compound of the present invention, it is possible to obtain an antibacterial superabsorbent resin having excellent antibacterial properties, coating stability and water absorption.

Superabsorbent polymer (SAP) is a material capable of forming a gel by absorbing 100 to 1000 times its own weight of water without being dissolved in water. In particular, sodium polyacrylate, which has undergone sodium neutralization treatment and crosslinking, is a representative superabsorbent resin, and it is the most successful superabsorbent resin in the market due to its low cost of raw materials and excellent water absorption.

Super absorbent polymers are used in various industrial fields such as diapers and various hygiene products, agriculture, and the petroleum industry. Among them, there are three criteria for judging the quality of super absorbent polymer for diapers:'Conservative ability (CRC)' that absorbs water while the baby is standing upright, and'Pressurized water that does not leak again even when sitting or lying down. It is the'absorption capacity (AUP)' and'solution permeability' that allows the secretion to be sufficiently absorbed down the diaper.

In order to improve the performance of the super absorbent polymer, a technology for crosslinking or coating the surface of the super absorbent polymer particles is being applied, and active research is underway. In the case of the currently commercialized super absorbent polymer, it is known that diol reacts with a carboxyl group (-COOH) on the surface of the super absorbent polymer to improve performance such as pressure absorption.

On the other hand, in the case of a super absorbent polymer used in hygiene products such as diapers, antibacterial action is important. However, a super absorbent polymer coated with a surface using diol has no antibacterial action at all. On the other hand, Korean Patent Laid-Open Patent No. 2018-0073335 adds copper oxide to a super absorbent polymer to provide antibacterial properties, and Chinese Patent Laid-Open No. 104987461 adds a chitosan derivative to a super absorbent polymer to impart antibacterial properties. In addition, there is also an invention in which an antimicrobial superabsorbent resin was prepared by introducing silver nanoparticles (Mingfang Chi et al.).

However, the antimicrobial superabsorbent resin containing copper oxide or silver nanoparticles as described above is harmful to the human body and the environment because it has an antimicrobial action by an elution method, and chitosan derivatives have a high molecular weight, so they have low binding strength with acrylic resins and have absorbency. There is a problem of lowering.

Therefore, there is a need for a super absorbent polymer that is harmless to the human body and has excellent antibacterial and absorbent properties.

Korean Patent Publication No. 2018-0073335 (published on July 2, 2018) Chinese Patent Publication No. 104987461 (published on October 21, 2015)

Mingfang Chi, et al., Antibacterial Superabsorbent Polymers from Tara Gum Grafted Poly(Acrylic acid) Embedded Silver Particles(2018), Polymers 2018, 10, 945

The polymer compound of the present invention has been devised to solve the above problems, and an object thereof is to provide a phenolic polymer compound having antimicrobial properties and a method for producing the same.

In addition, another object of the present invention is to provide an antimicrobial superabsorbent resin including the superabsorbent polymer and the antimicrobial phenolic polymer compound, and a method for producing the same.

In addition, it is another object of the present invention to provide a hygiene product comprising the antimicrobial superabsorbent resin.

The present invention can also aim to achieve these objects and other objects that can be easily derived by a person skilled in the art from the general description of the present specification, in addition to the above-described clear objects.

The antimicrobial phenolic polymer compound of the present invention is characterized in that it contains at least one or more repeating units represented by the following formula (1) in order to achieve the above-described object:

[Formula 1]

In Formula 1,

R ₁ , R ₂ , and R ₃ are each a hydrogen atom or a C6 to C20 linear alkyl group having 0 to 3 unsaturated bonds,

At least one of R ₁ , R ₂ , and R ₃ is the alkyl group,

m may be an integer of 1 to 1000, preferably 2 to 700, more preferably 2 to 400.

And, the alkyl group,

,

,

, C₁₅H₃₁, 또는 C₉H₁₉일 수 있다.

,

,

, C ₁₅ H ₃₁ , or C ₉ H ₁₉ .

In addition, the antimicrobial phenolic polymer compound may have a molecular weight of 400 to 20000, preferably 600 to 15000, and more preferably 800 to 10000.

On the other hand, the method for producing an antimicrobial phenolic polymer compound of the present invention,

(A) Reacting by mixing at least one compound represented by the following formula (2) or cashew nut shell oil with formaldehyde or a derivative thereof;

(B) Separating the product resulting from the reaction;

(C) Removing moisture from the separated product; And

(D) And removing the solvent from the product from which the moisture has been removed.

[Formula 2]

In Chemical Formula 2,

R ₁ , R ₂ , and R ₃ are each a hydrogen atom or a C6 to C20 linear alkyl group having 0 to 3 unsaturated bonds,

At least one of R ₁ , R ₂ , and R ₃ may be the alkyl group.

In addition, the compound represented by Formula 2 may be nonylphenol, pentadecylphenol, or cardanol.

In addition, the formaldehyde derivative may be paraformaldehyde, an aqueous formaldehyde solution, or formalin.

In addition, the step (A) may be characterized in that it proceeds under an acid catalyst.

And, the step (A),

100 mole parts of at least one compound or cashew nut shell oil represented by Formula 2;

65 to 100 mole parts, preferably 70 to 95 mole parts, more preferably 75 to 85 mole parts of the formaldehyde or a derivative thereof; And

0.7 to 1.5 mole parts of the acid catalyst, preferably 0.8 to 1.3 mole parts, more preferably 0.9 to 1.1 mole parts; may be characterized by reacting.

In addition, the acid catalyst may be oxalic acid, hydrochloric acid, sulfuric acid, salicylic acid, or a mixture thereof.

In addition, the step (A) may be characterized in that the reaction temperature is maintained at 90 to 180 °C, preferably 95 to 170 °C, more preferably 100 to 160 °C.

In addition, the step (A) may be characterized in that the reaction time is 2 to 9 hours, preferably 3 to 8 hours, more preferably 4 to 7 hours.

In addition, in the step (C), magnesium sulfate, silica, calcium sulfate, calcium chloride, or a mixture thereof may be used.

In addition, in the step (D), the solvent may be removed by distillation under reduced pressure.

Meanwhile, the antimicrobial superabsorbent resin of the present invention may include a superabsorbent polymer and the antimicrobial phenolic polymer compound.

In addition, the super absorbent polymer and the antimicrobial phenolic polymer compound may be characterized in that they form a covalent bond.

In addition, the super absorbent polymer and the antimicrobial phenolic polymer compound may form an ester bond (-COO-).

In addition, the antimicrobial superabsorbent resin,

100 parts by weight of the super absorbent polymer, and

5 to 20 parts by weight of the antimicrobial phenol-based polymer compound, preferably 7 to 15 parts by weight, more preferably 9 to 12 parts by weight.

In addition, the super absorbent polymer may be selected from the group consisting of acrylic resin, polyvinyl alcohol, polyacrylamide, polyethylene oxide, alginic acid, mixtures thereof, and copolymers thereof.

In addition, the average particle diameter of the antimicrobial superabsorbent resin may be 10 to 1000 μm, preferably 50 to 800 μm, more preferably 100 to 500 μm.

On the other hand, the method for producing an antimicrobial super absorbent polymer of the present invention,

(a) An addition step of adding an organic solvent to the antimicrobial phenolic polymer compound;

(b) A mixing/drying step of mixing and drying a super absorbent polymer with the antimicrobial phenolic polymer compound;

(c) After the mixing/drying step, a neutralization/washing step of neutralizing and washing the mixture; And

(d) After the neutralization/washing step, a redrying step of redrying the mixture may include.

And, with respect to 100 parts by weight of the super absorbent polymer, the antimicrobial phenolic polymer compound may be characterized in that 5 to 20 parts by weight, preferably 7 to 15 parts by weight, more preferably 9 to 12 parts by weight.

And, the step (b) or (d) may be characterized in that the drying temperature is 150 to 250 ℃, preferably 160 to 220 ℃, more preferably 170 to 190 ℃.

And, the step (b) or (d) may be characterized in that the drying time is 1 to 5 hours, preferably 1 to 4 hours, more preferably 2 to 3 hours.

In addition, step (c) may be characterized in that an organic solvent, a basic solution, and distilled water are sequentially used.

In addition, the organic solvent may be selected from the group consisting of chloroform, toluene, methylene chloride, tetrahydrofuran, alcohol, ether, or a mixture thereof.

In addition, the basic solution may be a sodium hydroxide solution, a potassium hydroxide solution, or a mixture thereof.

In addition, the formaldehyde index may be 0.01 to 0.5, 0.02 to 0.3, or 0.05 to 0.1.

On the other hand, the hygiene product of the present invention is characterized in that it contains the antibacterial super absorbent polymer.

The antimicrobial phenolic polymer compound according to the present invention is a compound having a plurality of phenol groups, and the hydroxy group (-OH) of the phenol forms a carboxyl group (-COOH) and an ester bond (-COO-) on the surface of the super absorbent polymer. It has excellent coating stability for super absorbent polymer.

In addition, the phenol and alkyl functional groups of the antimicrobial phenolic polymer compound have an antimicrobial action by a contact method, so that the antimicrobial action of the elution method is superior to that of the antibacterial action and is more environmentally friendly. In addition, since the antimicrobial phenolic polymer compound can be quickly dissolved in a coating solvent, it is easy to prepare a super absorbent polymer using it as a coating material.

On the other hand, the antimicrobial superabsorbent resin of the present invention has excellent antibacterial properties and absorbency by introducing the antimicrobial phenolic polymer compound, and can exhibit excellent performance when used in articles requiring absorbent performance such as diapers.

1 is an NMR spectrum of an antimicrobial phenolic polymer compound according to the present invention, N-CNSL, N-Cardanol, N-Nonylphenol, and N-PDP.
2 is an antimicrobial phenolic polymer compound according to the present invention, which is an IR spectrum of N-CNSL, N-Nonylphenol, and N-PDP.
3 is a GPC result of N-CNSL, N-Cardanol, N-Nonylphenol, and N-PDP as an antimicrobial phenolic polymer compound according to the present invention.
4 is a result of measuring the antimicrobial properties of the antimicrobial superabsorbent polymer prepared as an embodiment of the present invention.
5 is a measurement result of water absorption of an antimicrobial superabsorbent polymer prepared as an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail.

However, the following is only for describing in detail by exemplifying specific embodiments, and since the present invention may be variously changed and may have various forms, the present invention is not limited to the illustrated specific embodiments. It is to be understood that the present invention includes all changes, equivalents, and substitutes included in the spirit and scope of the present invention.

In addition, in the following description, there are many specific matters such as specific elements, etc., which are provided only to help a more general understanding of the present invention, and the present invention can be practiced without these specific matters. It is self-evident to those who have the knowledge of Further, in describing the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the subject matter of the present invention, the detailed description thereof will be omitted.

In addition, terms used in the present application are only used to describe specific embodiments, and are not intended to limit the present invention. Unless otherwise defined, all terms, including technical and scientific terms, used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. Terms as defined in a commonly used dictionary should be interpreted as having a meaning consistent with the meaning in the context of the related technology, and should not be interpreted as an ideal or excessively formal meaning unless explicitly defined in this application. Does not.

In this application, expressions in the singular include plural expressions unless the context clearly indicates otherwise.

In the present application, terms such as'include','include', or'have' are intended to refer to the presence of features, elements (or constituents), etc. described in the specification, but one or more other features or It does not mean that the component or the like does not exist or cannot be added.

In this application, the'formaldehyde index' is defined as follows:

Formaldehyde index

= (Number of moles of formaldehyde or its derivative / Number of moles of compound represented by Formula 2 or cashew nut shell oil)

× (weight of antimicrobial phenolic polymer compound / weight of super absorbent polymer).

The present invention relates to an antimicrobial phenolic polymer compound having a new chemical structure, and includes at least one or more repeating units represented by the following formula (1).

In Formula 1, R ₁ , R ₂ , and R ₃ may each be a hydrogen atom or a C6 to C20 linear alkyl group having 0 to 3 unsaturated bonds, and the unsaturated bond may be a double bond. In addition, at least one of R ₁ , R ₂ , and R ₃ may be the alkyl group other than a hydrogen atom.

Including at least one or more repeating units represented by Formula 1 means that one type of monomer or two or more types of monomers may be randomly repeated. Accordingly, the polymer compound may be a polymer in which one repeating unit is repeated, or a random copolymer in which repeating units of different structures are randomly repeated.

,

, 또는

이거나 이들의 이성질체일 수 있고, 포화 결합으로만 이루어진 경우 직쇄형의 C₁₅H₃₁, 또는 C₉H₁₉일 수 있다. And, the alkyl group

,

, or

Or it may be an isomer thereof, and may be a straight-chain C ₁₅ H ₃₁ , or C ₉ H ₁₉ when consisting only of a saturated bond.

As shown in Chemical Formula 1, a phenol group having an alkyl group as a repeating unit can exhibit an antibacterial effect on its own. Unlike a metal material that has an antibacterial action by an elution method, a polymer compound is used to provide an antibacterial action in a contact method to protect the human body and environment. It can reduce the harmfulness to The harmlessness to the human body is an important evaluation factor in hygiene products such as diapers, which are the main products of the super absorbent polymer, and it is possible to manufacture hygiene products with increased safety by using the antibacterial super absorbent polymer of the present invention.

In addition, in Formula 1, m may be an integer of 1 to 1000, preferably 2 to 700, more preferably 2 to 400. It can be easily dissolved in the coating solvent within the above range, so that the coating process can be facilitated.

In addition, the molecular weight of the antimicrobial phenolic polymer compound may be 400 to 20000, preferably 600 to 15000, more preferably 800 to 10000. When the molecular weight is less than the above range, coating stability for the super absorbent polymer may be deteriorated due to a decrease in the phenol functional group of the polymer chain and a reduction in the crosslinking effect of the novolac resin. On the other hand, when the molecular weight exceeds the above range, crosslinking may occur during the synthesis process of the antimicrobial phenolic polymer compound, and manufacturing may be difficult.

On the other hand, the method for producing an antimicrobial phenolic polymer compound of the present invention,

(A) Reacting by mixing at least one compound represented by the following formula (2) or cashew nut shell oil with formaldehyde or a derivative thereof;

(B) Separating the product resulting from the reaction;

(C) Removing moisture from the separated product; And

(D) It may include; removing the solvent from the product from which the moisture has been removed.

In Formula 2, R ₁ , R ₂ , and R ₃ are each a hydrogen atom or a C6 to C20 linear alkyl group having 0 to 3 unsaturated bonds, and at least one of R ₁ , R ₂ , and R ₃ is the above It may be an alkyl group.

In step (A), the reactant reacted with formaldehyde or a derivative thereof may be one of the compounds represented by Formula 2 or a mixture of two or more compounds represented by Formula 2. When one type of compound is reacted, the polymer compound produced can be a polymer in which one monomer is repeated, and when a mixture of two or more compounds is reacted, a random copolymer in which two or more monomers are randomly repeated Can be.

,

,

일 수 있고, 포화 결합으로만 이루어진 경우 C₁₅H₃₁, 또는 C₉H₁₉일 수 있다. And, the alkyl group

,

,

May be, if it consists only of saturated bonds It may be C ₁₅ H ₃₁ , or C ₉ H ₁₉ .

The compound represented by Formula 2 may be nonylphenol (NP), pentadecylphenol (PDP), or cardanol.

Meanwhile, the cashew nut shell liquid (CNSL) is an oil produced from cashew nut shell, and the antimicrobial phenolic polymer compound of the present invention using cashew nut shell oil is economically advantageous and simplifies the process by using cheap raw materials. can do. The main components of the cashew nut shell oil are Cardanol, Anacardic acid, Cardol, 2-Methyl cardol, or derivatives thereof.

,

,

, 또는

일 수 있다.The alkyl group or alkenyl group of the cardanol, anacardic acid, cardol, 2-methyl cardol, or derivatives thereof,

,

,

, or

Can be

The compound represented by Formula 2 or a substance capable of reacting with a phenolic compound such as cashew nut shell oil may be a formaldehyde derivative as well as formaldehyde, and a polymer chain may be formed by a condensation reaction thereof. The formaldehyde derivative may be paraformaldehyde, an aqueous formaldehyde solution, or formalin.In particular, paraformaldehyde is a polymer form of formaldehyde, a compound that decomposes again into formaldehyde at high temperatures, and the It is advantageous for preparing an antimicrobial polymer compound. As an example of the reaction, the reaction of pentadecylphenol (PDP) and paraformaldehyde may be expressed as in Scheme 1 below.

[Scheme 1]

Meanwhile, the reaction of at least one compound represented by Formula 2 or cashew nut shell oil and formaldehyde or a derivative thereof may be carried out under an acid catalyst, and a phenol resin prepared under an acid catalyst is referred to as a novolac resin. At this time,

100 mole parts of at least one compound or cashew nut shell oil represented by Formula 2;

65 to 100 mole parts, preferably 70 to 95 mole parts, more preferably 75 to 85 mole parts of the formaldehyde or a derivative thereof; And

0.7 to 1.5 mole parts of the acid catalyst, preferably 0.8 to 1.3 mole parts, more preferably 0.9 to 1.1 mole parts; can be reacted.

When the molar part of formaldehyde or its derivative is less than the above range, a polymer having a very low molecular weight can be obtained, whereas when it exceeds the above range, a polymer of other physical properties such as a resol resin can be easily crosslinked. I can.

In addition, if the molar part of the acid catalyst is less than the above range, the catalytic effect may be reduced, resulting in a decrease in the reaction rate and a decrease in the conversion rate. On the other hand, if it exceeds the above range, the production cost and purification cost increase, and side reactions occur. Problems may appear.

The acid catalyst may be oxalic acid, hydrochloric acid, sulfuric acid, salicylic acid, or a mixture thereof, but is not limited thereto, and a person skilled in the art may employ an appropriate acid catalyst.

In addition, the reaction of at least one compound represented by Chemical Formula 2 or cashew nut shell oil with formaldehyde or a derivative thereof is performed at a reaction temperature of 90 to 180°C, preferably 95 to 170°C, more preferably 100 to 160°C. Can be maintained. When the reaction temperature is less than the above range, water generated during the reaction cannot be effectively removed, whereas when the reaction temperature exceeds the above range, a crosslinking reaction of the reactant may occur at a high temperature.

In addition, the reaction time may be 2 to 9 hours, preferably 3 to 8 hours, more preferably 4 to 7 hours. If the reaction time is less than the above range, the conversion rate of the reaction may be lowered, whereas if the reaction time exceeds the above range, the efficiency compared to the reaction time may decrease.

After the reaction between the phenolic compound and formaldehyde or a derivative thereof proceeds, the reaction product is separated. After the reaction product, distilled water and chloroform are put in a separatory funnel, the chloroform layer may be collected to separate the product. After the product is separated, it is preferable to use magnesium sulfate, silica, calcium sulfate, calcium chloride or a mixture thereof to remove the remaining fine moisture and remove the moisture. After that, the solvent is removed, and the solvent can be easily removed by distillation under reduced pressure.

On the other hand, the antimicrobial superabsorbent resin of the present invention is obtained by modifying the surface of a superabsorbent polymer (SAP) by using the antimicrobial phenolic polymer compound as a coating material. The superabsorbent resin is a material capable of absorbing water through the interaction between a hydrophilic group in a polymer and a water molecule, and has a carboxyl group (-COOH), a representative hydrophilic group, and has a very high affinity for water. In addition, when the carboxyl group is neutralized by sodium hydroxide or the like and has a charge, ions and attractive force act through electrostatic force, and the ions accompany a large amount of water molecules, thereby increasing absorption.

The super absorbent polymer may be a synthetic polymer or a natural polymer, and may be selected from the group consisting of acrylic resin, polyvinyl alcohol, polyacrylamide, polyethylene oxide, alginic acid, mixtures thereof, and copolymers thereof.

The antimicrobial phenolic polymer compound of the present invention contains a large amount of hydroxy group (-OH) of phenol, and thus can form a bond with the functional group of a super absorbent polymer. In particular, the hydroxy group (-OH) is a super absorbent polymer. It is easy to form an ester (-COO-) bond with the carboxyl group (-COOH) of. In addition, by using a polymer chain having antibacterial properties as a coating material, they can stably exist by forming a hydrophobic film on the outside of the super absorbent polymer.

In general, chitosan, which is a material that can be used to impart antimicrobial properties, participates in acrylic polymerization and crosslinks acrylics with each other, so that it has poor hygroscopicity and has a large molecular weight, so it is difficult to bind with the carboxyl group of the acrylic resin. In contrast, in the case of the antimicrobial superabsorbent resin of the present invention, due to the structure of the antimicrobial material and the interaction between the antimicrobial material and the superabsorbent resin, coating stability is very excellent and hygroscopicity compared to the superabsorbent resin modified with a material such as metal or chitosan. I can keep it.

Moreover, chitosan participates in acrylic polymerization and can cross-link acrylics with each other, so that it has poor hygroscopicity and has a large molecular weight, so it is difficult to bind with the carboxyl group of the acrylic resin.

The antimicrobial superabsorbent resin may include 100 parts by weight of the superabsorbent polymer, and 5 to 20 parts by weight, preferably 7 to 15 parts by weight, more preferably 9 to 12 parts by weight of the antimicrobial phenolic polymer compound. . When the weight part of the antimicrobial phenolic polymer compound is less than the above range, the antibacterial effect may be lowered because the coating is not uniform due to insufficient polymer compound. On the other hand, when it exceeds the above range, the coating thickness on the surface of the super absorbent polymer becomes thick. Absorption performance may be poor.

In addition, the average particle diameter of the antimicrobial superabsorbent resin may be 10 to 1000 μm, preferably 50 to 800 μm, more preferably 100 to 500 μm. If the average particle diameter of the antimicrobial superabsorbent resin is less than the above range, the antimicrobial substance may elute out of the packaging material in the product to which the superabsorbent polymer is actually applied, which may be harmful to the human body or the environment, while the average particle diameter is within the above range. When exceeding, the absorption performance may be lower than the antimicrobial superabsorbent resin within the above range.

On the other hand, the method for producing an antibacterial super absorbent polymer of the present invention,

(a) An addition step of adding an organic solvent to the antimicrobial phenolic polymer compound;

(b) A mixing/drying step of mixing and drying a super absorbent polymer with the antimicrobial phenolic polymer compound;

(c) After the mixing/drying step, a neutralization/washing step of neutralizing and washing the mixture; And

(d) After the neutralization/washing step, a redrying step of redrying the mixture is included.

First, an organic solvent such as chloroform is poured into the antimicrobial phenolic polymer compound and mixed well (step (a)), and then a super absorbent polymer is added to the antimicrobial phenolic polymer compound and mixed. After the sample is well mixed, it is spread on a glass plate and dried (step (b)), wherein the drying temperature may be 150 to 250°C, preferably 160 to 220°C, more preferably 170 to 190°C. If the drying temperature is less than the above range, the coating reaction may not be accelerated and the coating efficiency may be deteriorated. On the other hand, if the drying temperature exceeds the above range, there may be a problem that the super absorbent polymer and the superabsorbent polymer are decomposed by oxidation and heat.

In addition, the drying time may be 1 to 5 hours, preferably 1 to 4 hours, more preferably 2 to 3 hours. If the drying time is less than the above range, the coating reaction does not sufficiently proceed and the coating efficiency is deteriorated. On the other hand, if the drying time exceeds the above range, unnecessary time is wasted, and the superabsorbent polymer may be deteriorated.

On the other hand, with respect to 100 parts by weight of the superabsorbent polymer, the antimicrobial phenolic polymer compound may be 5 to 20 parts by weight, preferably 7 to 15 parts by weight, and more preferably 9 to 12 parts by weight. When the weight part of the antimicrobial phenolic polymer compound is less than the above range, the antibacterial effect may be lowered because the coating is not uniform due to insufficient polymer compound. On the other hand, when it exceeds the above range, the coating thickness on the surface of the super absorbent polymer becomes thick. Absorption performance may be poor.

After the drying is completed, neutralization and washing of the mixture are performed (step (c)). In this case, an organic solvent, a basic solution, and distilled water may be used in sequence. The organic solvent may be selected from the group consisting of chloroform, toluene, methylene chloride, tetrahydrofuran, alcohol, ether, or a mixture thereof, but is not limited thereto, and an appropriate organic solvent may be used. In addition, the basic solution may be a sodium hydroxide solution or a potassium hydroxide solution.

After neutralization and washing of the mixture, the mixture is dried again (step (d)), wherein the range of the drying temperature and drying time is the same as in step (b).

In the present invention, the formaldehyde index may be 0.01 to 0.5, 0.02 to 0.3, or 0.05 to 0.1.

The'formaldehyde index' is defined as follows:

Formaldehyde index

= (Number of moles of formaldehyde or its derivative / Number of moles of compound represented by Formula 2 or cashew nut shell oil)

×( Weight of antimicrobial phenolic polymer compound / weight of super absorbent polymer).

When the formaldehyde index is less than the above range, an antimicrobial phenolic polymer compound having a very low molecular weight may be obtained or the coating may not be uniform, so that the antibacterial effect may be lowered.On the other hand, when it exceeds the above range, crosslinking may occur more easily. An antimicrobial phenolic polymer may be obtained, or the absorption performance may be degraded due to a thick coating thickness on the surface of the super absorbent polymer.

On the other hand, the hygiene product of the present invention includes the antibacterial superabsorbent resin, and the hygiene product refers to a diaper, a sanitary napkin, and other articles requiring absorption performance.

Hereinafter, an embodiment of the present invention will be described.

Example

Produce Yes 1: Synthesis of antimicrobial phenolic polymer compound N-CNSL

2.00 g of Cashew Nut Shell Liquid (CNSL), 0.158 g of paraformaldehyde, and 0.006 g of oxalic acid were added to a round bottom flask and reacted at 120° C. for 6 hours while stirring. The synthesized resin, 150 ml of distilled water, and 150 ml of chloroform were placed in a separatory funnel and shaken 4 to 5 times, and the chloroform layer in which the resin was dissolved was collected through extraction. Thereafter, the remaining fine moisture was removed using magnesium sulfate (MgSO ₄ ). The remaining solution was put in a vial, and the solvent was removed by distillation under reduced pressure to obtain a synthesized polymer N-CNSL.

Preparation Example 2: Synthesis of antimicrobial phenolic polymer compound N-Cardanol

CNSL of Preparation Example 1 was replaced with cardanol to obtain a polymer N-Cardanol as a product by the same method.

Preparation Example 3: Synthesis of antimicrobial phenolic polymer compound N-Nonylphenol

CNSL of Preparation Example 1 was replaced with Nonylphenol (NP) to obtain a polymer N-Nonylphenol as a product in the same manner.

Preparation Example 4: Synthesis of antimicrobial phenolic polymer compound N-PDP

CNSL of Preparation Example 1 was replaced with pentadecylphenol (PDP) to obtain a polymer N-PDP as a product by the same method.

Test Example 1: Identification of the synthesized antimicrobial phenolic polymer compound

The antimicrobial phenolic polymer compound synthesized in Preparation Examples 1 to 4 was analyzed by NMR (FIG. 1), IR (FIG. 2), and GPC (FIG. 3) to confirm that the synthesis was successful.

Preparation Example 5: Synthesis of super absorbent polymer (SAP)

After inserting a cotton ball and a 0.45 μm filter into a 25 ml syringe (Syringe), Basic alumina was put, and then 20 g of acrylic acid was filtered to remove the inhibitor. Then, a 1 L beaker was placed on a container containing ice, and 25 ml of a 33% NaOH solution was added. Thereafter, acrylic acid was added by Dropwise and stirred for 15 minutes so that the solution became uniform. To the well-mixed solution, 0.5 ml of polyethylene glycol diacrylate (PEGDA) from which the inhibitor was removed was added and stirred for another 10 minutes. Then, 0.2 g of ascorbic acid and 0.2 ml of hydrogen peroxide were sequentially added, and the reaction was carried out in a reactor at 99° C. for 5 minutes. The gelled product was cut into small sizes, spread on a glass plate, reacted and dried in an oven at 180° C. for 2 hours, and the dried product was ground with a grinder and filtered to obtain a super absorbent polymer (SAP) of an appropriate size. This SAP was again put into a 500 ml beaker, and 200 ml of a 1 M HCl solution was poured and stirred for 30 minutes. Afterwards, the acid-treated SAP was washed with 250 ml of 1 M HCl solution and 1500 ml of distilled water in sequence, spread on a glass plate, and dried in an oven at 180° C. for 2 hours.

Example 1: Synthesis of antimicrobial super absorbent polymer coated with N-CNSL

0.1 g of the antimicrobial phenolic polymer compound N-CNSL synthesized in Preparation Example 1 was put in a vial, 0.4 ml of chloroform was poured, and mixed well. Thereafter, 1 g of SAP obtained in Preparation Example 5 was put into a vial containing the N-CNSL and mixed again using a vortex mixer, and then spread on a glass plate and dried in an oven at 180° C. for 2 hours. After drying is completed, neutralization and washing are performed sequentially using 500 ml of chloroform, 500 ml of 1 M sodium hydroxide solution, and 500 ml of distilled water, and then dried in an oven at 180° C. for 2 hours, and coated with N-CNSL. I got a resin.

Example 2: Synthesis of antimicrobial super absorbent polymer coated with N-Cardanol

An antimicrobial superabsorbent resin coated with N-Cardanol was prepared in the same manner by replacing N-CNSL of Example 1 with N-Cardanol synthesized in Preparation Example 2.

Example 3: Synthesis of antibacterial superabsorbent polymer coated with N-Nonylphenol

N-CNSL of Example 1 was replaced with N-Nonylphenol synthesized in Preparation Example 3, and an antimicrobial superabsorbent resin coated with N-Nonylphenol was prepared in the same manner.

Example 4: Synthesis of antibacterial super absorbent polymer coated with N-PDP

The N-CNSL of Example 1 was replaced with the N-PDP synthesized in Preparation Example 4, and an antimicrobial superabsorbent resin coated with N-PDP was prepared in the same manner.

Comparative Example 1: Synthesis of super absorbent polymer coated with propanediol

N-CNSL of Example 1 was replaced with propanediol (1,3-Propanediol, PD), and a superabsorbent polymer modified with propanediol was prepared in the same manner.

Test Example 2: Measurement of antimicrobial properties of antimicrobial superabsorbent polymer

The antimicrobial superabsorbent resin prepared in Examples 1 to 4 was dissolved in chloroform at 1 to 5 wt% on a silicon wafer, and then spin-coated at 3000 rpm for 30 seconds, and the chloroform was evaporated for 24 hours to obtain an antimicrobial super absorbent resin sample. . As a loading step, the sample was transferred to a Petri dish, and 100 μl of a 10 ⁶ CFU/ml bacterial solution was dropped thereon, and then covered with an OHP film. The loading sample was placed in a culture vessel with humidity so that the bacterial solution did not evaporate by laying a tissue moistened with water, and the bacteria were cultured for 24 hours in a shaking incubator set at 37°C. After the cultivation was completed, the OHP film was removed, and the bacterial solution remaining in the film and the sample was repeatedly washed several times with 900 μl of sodium chloride solution so that bacteria could be dispersed in the solution. At the end of this washing process, assuming 0% antimicrobial activity, theoretically, 10 ⁵ CFU/ml of solution remains on the Petri dish. After washing, collect the solution in which the bacteria are dispersed, make a 10 ² , 10 ³ CFU/ml solution, drop 100 μl each onto the Agar medium, spread it well on the medium using a glass spreader, and place it in an incubator set at 37 ℃. And incubated for 18 hours. After the cultivation was completed, the number of bacterial colonies grown on the Agar medium was counted to confirm the presence and strength of antimicrobial activity. It showed antibacterial properties (Fig. 4).

Test Example 3: Measurement of water absorption of antimicrobial superabsorbent polymer

Antimicrobial superabsorbent resin (N-CNSL, N-Cardanol, N-NP, N-PDP) prepared in Examples 1 to 4, super absorbent polymer (PD) prepared in Comparative Example 1, and prepared in Preparation Example 5 Each 0.1 g of the super absorbent polymer (Pristine) was put in a Falcon tube, and then 50 ml of distilled water was poured and shaken well. The Falcon tube was placed in a tray and placed on a flat surface to allow the resin to absorb enough water for an hour. Water that was not absorbed was filtered through a sieve for 1 minute, and the weight of the resin absorbing water was measured to confirm water absorption (FIG. 5). N-Cardanol and N-PDP showed an absorption capacity of about 11000 to 12000%, and N-CNSL and N-NP showed an absorption capacity of 6000 to 7000%. For reference, pristine is not coated and PD is only modified to improve pressure absorption, so neither has antibacterial properties.

In the above, preferred embodiments of the present invention have been described, but the present invention is not limited to the specific embodiments described above, and those of ordinary skill in the art can implement various modifications without departing from the gist of the present invention. Of course it is possible. Therefore, the scope of the present invention should not be construed as limited to the above embodiments, and should be defined by the claims and equivalents to the claims described later.

CNSL: Cashew Nut Shell Liquid

Claims (10)

An antimicrobial phenolic polymer compound containing at least one or more repeating units represented by the following formula (1):
[Formula 1]

In Formula 1,
R ₁ , R ₂ , and R ₃ are each a hydrogen atom or a C6 to C20 linear alkyl group having 0 to 3 unsaturated bonds,
At least one of R ₁ , R ₂ , and R ₃ is the alkyl group,
m is an integer of 1 to 1000, 2 to 700, or 2 to 400. The method according to claim 1,
The antibacterial phenolic polymer compound has a molecular weight of 400 to 20000, 600 to 15000, or 800 to 10000. (A) reacting by mixing at least one compound represented by the following formula (2) or cashew nut shell oil with formaldehyde or a derivative thereof;
(B) separating the product resulting from the reaction;
(C) removing moisture from the separated product; And
(D) removing the solvent from the moisture-removed product; characterized in that it comprises, the method for producing an antimicrobial phenolic polymer compound.
[Formula 2]

In Chemical Formula 2,
R ₁ , R ₂ , and R ₃ are each a hydrogen atom or a C6 to C20 linear alkyl group having 0 to 3 unsaturated bonds,
At least one of R ₁ , R ₂ , and R ₃ is the alkyl group. The method of claim 3,
The step (A) is a method for producing an antimicrobial phenolic polymer compound, characterized in that it proceeds under an acid catalyst. A super absorbent polymer comprising a super absorbent polymer and the antimicrobial phenolic polymer compound of claim 1 or 2. The method of claim 5,
The antimicrobial superabsorbent resin,
100 parts by weight of the super absorbent polymer, and
5 to 20 parts by weight, 7 to 15 parts by weight, or 9 to 12 parts by weight of the antimicrobial phenol-based polymer compound. The method of claim 5,
The super absorbent polymer is selected from the group consisting of acrylic resin, polyvinyl alcohol, polyacrylamide, polyethylene oxide, alginic acid, mixtures thereof, and copolymers thereof. (a) an addition step of adding an organic solvent to the antimicrobial phenolic polymer compound of claim 1 or 2;
(b) mixing/drying step of mixing and drying a super absorbent polymer with the antimicrobial phenolic polymer compound;
(c) after the mixing/drying step, a neutralization/washing step of neutralizing and washing the mixture; And
(D) after the neutralization/washing step, a re-drying step of re-drying the mixture; containing, a method for producing an antibacterial super absorbent polymer. The method of claim 8,
The step (c) is a method for producing an antimicrobial superabsorbent polymer, characterized in that sequentially using an organic solvent, a basic solution and distilled water. A hygiene product comprising the antimicrobial superabsorbent polymer of any one of claims 5 to 7.

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